Phosphorohydrazidothioates



United States Patent M PHOSPHOROHYDRAZDOTHIOATES Henry Tolkmith,Midland, Mich., assi'gnor to The Dow Chemical Company, Midland, Mich., acorporation of Delaware No Drawing. Filed Oct. 28, 1959, Ser. No.849,190

6 Claims. (Cl. 260-461) The present invention is directed tophosphorohydrazidothioates corresponding to the formula R 8 \ll In thisand succeeding formulae, each R represents lower alkoxy or di(loweralkyl)-amino, and R represents a radical selected from the groupconsisting of in which X represents lower alkanoyl or benzoyl, Yrepresents oxygen or sulfur and Z represents lower alkyl, lower alkenyl,cyclohexyl or phenyl. The expressions lower alkyl, lower alkanoyl andlower alkeny are employed in the present specification and claims torefer to radicals containing from lcarbon atoms, inclusive. These newcompounds are liquid or crystalline solid materials which are somewhatsoluble in many organic soli with an isocyanate having the formulaY=C=N-Z wherein R, Y and Z are as previously defined. The reactionpreferably is carried out in an inert organic liquid as reaction medium.Good results are obtained when employing substantially equimolecularproportions of the reagents. The reaction is somewhat exothermic andtakes place smoothly at temperatures of from 0 to 80 C. with theformation of the desired product. The temperature may be controlled byregulating the rate of contacting the reactants and by external cooling.In carrying out the reaction, the reactants may be mixed together in anyconvenient manner. action, any reaction medium may be removed byevaporation to obtain the desired product as a residue. This product maybe purified by conventional means such as extraction withsuitablesolvents and recrystallization.

: The acyl substituted phosphorohydrazidothioates of the Upon completionof the re- 2,965,668 Patented Dec. 20, 1960 present invention may beprepared by reacting a phosphorohydrazidothioate corresponding to theformula Ii NH-NHs with an acyl halide of the formula bromine X-{ orchlorine wherein R and X are as previously defined. The reaction iscarried out in the presence of an alkaline reagent such as a tertiaryamine and preferably in an inert organic liquid as reaction medium. Goodresults are obtained when one molecular proportion of thephosphorohydrazidothioate reagent is reacted with 1, 2 or 3 molecularproportions of the acyl halide and in a corresponding amount of thealkaline reagent depending upon whether it is desired to introduce l, 2or 3 acyl groups into the molecule. The reaction is somewhat exothermicand takes place smoothly at the temperature range of from 0 to C. withthe production of the desired product and hydrogen halide of reaction.This hydrogen halide appears in the reaction mixture as the halide ofthe alkaline reagent such as tertiary amine hydrogen halide. Thetemperature may be controlled by regulating the rate of contacting thereagents and by external cooling. In carrying out the reaction, thereactants may be mixed together in any convenient manner and in thepresence of the alkaline reagent. Upon completion of the reaction, thereaction mixture may be washed with water to remove halide of reaction,and any reaction medium removed by evaporation to obtain the desiredproduct as a residue. This product may be purified by conventionalprocedures such as recrystallization or extraction with suitablesolvents.

The following examples merely illustrate the invention and are not to beconstrued as limiting.

Example 1.-0,0-dimethyl 2-phenylcarbam0yl phosphorohydrazidothioatePhenyl isocyanate (48 grams; 0.4 mole) was dispersed in 300 millilitersof benzene and the resulting mixture added slowly portionwise to 63grams (0.4 mole) of 0,0- dimethyl phosphorohydrazidothioate dispersed in300 milliliters of benzene. The addition was carried out at roomtemperature and over a period of 3 hours with stirring. During theaddition, an 0,0-dimethyl Z-phenylcarbamoyl phosphorohydrazidothioateproduct precipitated in the reaction mixture as a crystalline solid.Following the reaction, the product was separated by filtration andrecrystallized from diethyl ether. The recrystallized product melted at10l-l02 C. and had nitrogen, phosphorus and sulfur contents of 14.8percent, 11.84 percent and 11.79 percent, respectively, as compared totheoretical contents of 15.27 percent, 11.25 percent and 11.65 percent.

Example 2.0,0-diethyl Z-phenylcarbamoyl phosphorohydrazidothioate memes:

cate product melting at 145 C. and containing nitrogen, phosphorus andsulfur contents of 13.17 percent, 10.68 percent and 10.98 percent,respectively as compared to theoretical contents of 13.85 percent, 10.02percent and 10.57' percent.

Example 3.0,0-dinzethyl Z-allvlthiocarbamoyl phosphorohydrazidothioateIn a manner exactly as described in Example 1, 0.4 mole of allyliso-thiocyanate was reactedwith 0.4 mole of 0,0-dimethylphospho-rohydrazidothioate. Following the reaction, an 0,0-dimethylZ-allylthiocarbamoyl phosphorohydrazidothioate product was separatedfrom the reaction mixture by filtration and recrystallized from diethylether. The recrystallized product melted at 110 111 C. and had nitrogen,phosphorus and sulfur contents of 16.61 percent, 12.47 percent and 25.1percent, respectively, as compared to theoretical contents of 16.4percent, 12.13percent and 25.12 percent.

Example 4.-0,0-dietlzyl 2-allylthz'ocarbamoyl phosphorohydrazidothioateAllyl isothiocyanate (40 grams; 0.4 mole) was dispersed in 500milliliters of benzene and the resulting mix ture added portionwise to0.4 mole of 0,0-diethyl phosphorohydrazidothioate dispersed in 400milliliters of benzene The addition was carried out with stirring atroom temperature and over a period of 3 hours. Following theaddition,the benzene was removed from the reaction mixture by evaporation and theresidue recrystallized from diethyl ether to obtain an 0,0-diethyl2-allylthiocarbamoyl phosphorohydrazidothioate product as a crystallinesolid melting at 114-115 C. This product had nitrogen, phosphorus andsulfur contents of 14.67 percent, 11.0 percent and 22.4 percent,respectively, as compared to theoretical contents of 14.83 percent,10.93 percent and 22.63 percent.

Example 5 .--0,0-dimethyl 2-phenylthi0carbam0ylphosphorohydrazidothioate In a similar manner, 54 grams (0.4 mole) ofphenyl isothiocyanate was reacted with 0.4 mole of 0,0-dimethylphosphorohydrazidothioate. The conditions of reaction and methods ofseparation were all as described in Example 4 with an 0,0-dimethyl2-phenylthiocarbamoyl phosphorohydrazido-thioate product being obtainedas a crystalline solid melting at 104105 C. This product containednitrogen, phosphorus and sulfur contents of 14.17 percent, 10.67 percentand 22.4 percent, respectively, as compared to theoretical contents of14.42 percent, 10.63 percent and 22.01 percent.

Example 6.-0,0-diethyl Z-phenylthiocarbamoyl phosphorohydrazidothioateIn a manner exactly as described in Example 4, 0.4 mole of phenylisothiocyanate was reacted with 0.4 mole of 0,0-diethylphosphorohydrazidothioate to obtain an 0,0-diethyl 2-phenylthiocarbamoylphosphorohydrazidothioate product as a crystalline solid melting at 121-122 C. This product had nitrogen, phosphorus and sulfur contents of13.09 percent, 9.94 percent and 20.83 percent, respectively, as comparedto theoretical contents of 13.16 percent, 9.7 percent and 20.08 percent.

Example 7.-0,0-diethyl 2-cyclohexylthiocarbamoylphosphorohydrazidothioaze 4 Cyclohexyl isothiocyanate (50 grams; 0.4mole) was reacted with 0.4 mole of 0,0-diethyl phosphorohydrazrdotbioateas described in Example 4. The cond tio s of reactions and methods ofseparation were as'descn'bed in the example with the desired productbeing recrystallized from cyclohexane. As a result of these operations,an 0,0-diethyl 2-cyclohexylthiocarbamoyl phosphorohydrazidothioateproduct was obtained as a crystalline solid melting at 82-84 C., andhaving nitrogen, phosphorus and sulfur contents of 12.9 percent, 10.39percent and 11.09' percent, respectively, as compared to theoreticalcontents of 13.58 percent, 10.01 percent and. 10.37 percent.

Example 8.N,N,N',N-tetramethyl 2- phenylthiocarbamoylphosphorohydrazidothioate Phenyl isothiocyanate (0.16 mole) wasdispersed in 200 milliliters of benzene and the resulting mixture addedportionwise to 29 grams (0.16 mole) ofN,N,N,N'-tetramethylphosphorohydrazidothioate dispersed in 200milliliters of benzene. The addition was carried out at room temperatureand over a period of 3 hours with stirring. During the addition, anN,N,N',N-tetramethyl 2-pheny1- thiocarbamoyl phosphorohydrazidothioateproduct precipitated in the reaction mixture as a crystalline solid.Following the reaction, this product was separated by filtration andrecrystallized from diethyl ether. Therecrystallized product melted at134-134.5 C;, and 'contained nitrogen, phosphorus and sulfur contents of21.69 percent, 9.92 percent and 20.57 percent, respectively, as comparedto theoretical contents of 22.07 percent, 9.76 percent and 20.2 percent.

Example 9.--0,0-dimethyl Z-acetyl phosphorohydrazidothioate Acetylchloride (32 grams; 0.41 mole) was dispersed in 300 milliliters ofbenzene and the resulting mixture added portionwise to a mixturecomprising 0.4 mole of 0,0-dimethyl phosphorohydrazidothioate and 0.41mole of triethylamine dispersed in 500 milliliters of benzene. Theaddition was carried out at room temperature and over a period of 3hours with stirring. During the addition, a solid material precipitatedin the reaction mixture. Following the reaction, the solid was separatedby filtration and successively extracted with benzene and diethyl ether.The benzene and ether extracts and the filtrate were then combined, andthe solvent removed by evaporation to obtain an 0,0-dimethyl 2-actylphosphorohydrazidothioate product as a crystalline residue. This productwas recrystallized from cyclohexane and found to melt at 96-97 C., andcontain nitrogen and sulfur contents of 13.65 percent and 16.48 percent,respectively, as compared to theoretical contents of 14.14 percent and16.18 percent. I

Example 10.-0,0-dimethyl Z-benzoyl phosphorohydrazidothioate CHr-Ophorus and sulfur contents of 10.66 percent, 11.97 percent and 12.28percent, respectively, as compared to theoretical contents of 10.77percent, 11.9 percent and 12.32 percent. 7

Example 11.0,0-diethyl Z-acetyl phosphorohydrazidothioate Acetylchloride (0.4 mole) was reacted with 0.4 mole of 0,0-diethylphosphorohydrazidothioate in the presence of 0.41 mole of triethyl amineexactly as described in Example 9. As a result of these operations,there was obtained an 0,0-diethyl 2-acetyl phosphorohydrazidothioateproduct melting at 75 -76 C. and containing nitrogen, phosphorus andsulfur contents of 11.88 percent, 14.19 percent and 14.51 percent,respectively, as compared to theoretical contents of 12.38 percent,13.69 percent and 14.17 percent.

Example 12.-0,0-diethyl Z-benzoyl phosphorohydrazidothioate Benzoylchloride (0.4 mole) was reacted with 0.4 mole of 0,0-diethylphosphorohydrazidothioate in the presence of 0.41 mole of triethyl amineas described in Example 10. The conditions of reaction and methods ofseparation were all as therein set forth with an 0,0-diethyl 2- benzoylphosphorohydrazidothioate product being obtained as a crystalline solidmelting at 102-103 C. This product had nitrogen, phosphorus and sulfurcontents of 9.97 percent, 11.22 percent and 11.44 percent, respectively,as compared to theoretical contents of 9.72 percent, 10.74 percent and11.12 percent.

Example 13.0,0-diethyl 2,2-a'iacetyl phosphorohydrazidathioate Acetylchloride (47 grams; 0.6 mole) was dispersed in 700 milliliters ofbenzene and the resulting product added portionwise to a mixtureconsisting of 0.3 mole of 0,0-diethyl phosphorohydrazidothioate and 0.65mole of triethylamine dispersed in 300 milliliters of benzene. Theaddition was carried out over a period of 3 hours and at roomtemperature with stirring. Upon completion of the reaction, the reactionmixture was filtered and the solvent removed from the filtrate byevaporation. As a result of these operations, there was obtained an0,0-diethyl 2,2-diacetyl phosphorohydrazidothioate product as a liquidmaterial having nitrogen, phosphorus and sulfur contents of 10.03percent, 11.04 percent and 11.39 percent, respectively, as compared totheoretical contents of 10.44 percent, 11.55 percent and 11.95 percent.This product had a refractive index n/ D of 1.4868 at 25 C.

Example ]4.-0,0-aiethyl triacetyl phosphorohydrazidothioate Acetylchloride (94 grams; 1.2 moles) was dispersed in 800 milliliters ofbenzene and the resulting product added portionwise with stirring to amixture consisting of 0.4 mole of 0,0-diethyl phosphorohydrazidothioateand 0.4 mole of triethyl amine dispersed in 500 milliliters of benzene.The addition was carried out at room temperature and over a period ofabout 3 hours. Upon completion of the reaction, the reaction mixture wasfiltered, the solvent removed from the filtrate by evaporation and theresidue recrystallized from diethyl ether. As a result of theseoperations, there was obtained an 0,0-diethyl triacetylphosphorohydrazidothioate product as a crystalline solid melting at78-80 C. and having nitrogen, phosphorus and sulfur contents of 9.06percent, 10.41 percent and 10.71 percent, respectively, as compared totheoretical contents of 9.03 percent, 9.98 percent and 10.34 percent.

Example 15.0,0-dimethyl triacetyl phosphorohydra zidothioate CHr-O S OIn a similar manner, 1.2 moles of acetyl chloride was reacted with 0.4mole of 0,0-dimethyl phosphorohydrazidothioate in the presence of 1.2moles of triethyl amine exactly as described in Example 14. Uponcompletion of the reaction, the reaction mixture was processed as setforth therein to obtain an 0,0-dimethyl triacetylphosphorohydrazidothioate product as a crystalline solid melting at82-84 C., and containing nitrogen, phosphorus and sulfur contents of 9.9percent, 10.86 percent and 11.37 percent, respectively, as compared totheoretical contents of 9.93 percent, 10.97 percent and 11.36 percent.

In a similar manner other compounds of the present invention may beprepared as follows:

O-amyl O-methyl Z-methallylcarbamoyl phosphorohydrazidothioate byreacting methallyl isocyanate with O- amyl O-methylphosphorohydrazidothioate.

N,N-diethyl N,N'-diamyl Z-methylcarbamoyl phosphorohydrazidothioate byreacting methyl isocyanate with N,N-methy1 N',N-diamylphosphorohydrazidothio ate.

N-methyl N-ethyl N-propyl N-butyl Z-butylthiocarbamoylphosphorohydrazidothioate by reacting butyl isothiocarbamate withN-rnethyl N-ethyl N'-propyl N'-butyl phosphorohydrazidothioate.

0,0-dibutyl Z-amylcarbamoyl phosphorohydrazidothioate by reacting amylisocyanate with 0,0-dibutyl phosphorohydrazidothioate.

O-methyl O-ethyl 2-buten-2-ylcarbamoyl phosphorohydrazidothioate byreacting buten-Z-yl isocyanate with O-methyl O-ethylphosphorohydrazidothioate.

N,N,N,N-tetraethyl 2-propenylcarbamoyl phosphorohydrazidothioate byreacting 2-propenyl isocyanate with N,N,N,N-tetraethylphosphorohydrazidothioate.

N,N,N,N'-tetrarnethyl 2-cyclohexylcarbamoyl phosphorohydrazidothioate byreacting cyclohexyl isocyanate with N,N,N',N-tetramethylphosphorohydrazidothioate.

N,N,N',N'-tetramethyl 2-valeryl phosphorohydrazidothioate by reactingvaleryl bromide with N,N,N,N-tetramethyl phosphorohydrazidothioate inthe presence of tributylamine.

N,N-dimethyl N',N'-diethyl 2-propionyl phosphorohydrazidothioate byreacting propionyl chloride with N,N- dimethyl N',N-diethylphosphorohydrazidothioate in the presence of triethylamine.

O-butyl O-ethyl 2-butyryl phosphorohydrazidothioate by reacting butyrylbromide with O-butyl O-ethyl phosphorohydrazidothioate in the presenceof pyridine.

N,N,N,N tetraethyl 2-benzoyl phosphorohydrazidothioate by reactingbenzoyl chloride with N,N,N,N'- tetrarnethyl phosphorohydrazidothioatein the presence of triethyl amine.

The new compounds of the present invention are effective as herbicidesand parasiticides and are adapted to be employed for the control of manynoxious weeds and agricultural pests. For such use, the products may bedispersed on an inert finely divided solid and employed as dusts. Also,such mixtures may be dispersed in water with the aid of a surface activeagent, and the resulting aqueous suspensions employed as sprays. Inother procedures, the products may be employed as constituents ofoil-in-water emulsions or water dispersions with or without the additionof surface active dispersing agents. In representative operations, 100percent controls of mites are obtained with aqueous compositionscontaining 500 parts by weight of 0,0-diethyl 2-allylthiocarbamoylphosphorohydrazidothioate, per million parts by weight of ultimatecomposition. In other operations, 100 percent kills of canary grass areobtained with aqueous compositions containing 100 parts by weight of0,0-diethyl-2- cyclohexylthiocarbamoyl phosphorohydrazidothioate permillion parts by weight of ultimate mixture.

The 0,0-di(lower alkyl) phosphorohydrazidothioates andN,N,N,N'-tetra(lower alkyl) phosphorohydrazidothioates employed asstarting materials as herein described may be prepared in known methodsby reacting hydrazine hydrate with a suitable 0,0-di(lwer alkyl)phosphorochloridothioate or N,N,N',N'-tet1'a (lower alkyl)phosphorohydrazidothioate in the presence of an organic liquid asreaction medium. The reaction takes place smoothly at temperatures offrom 0 to 50 C. with the production of the desired product and hydrazinehydrochloride of reaction. Upon completion of the reaction, the desiredproduct may be separated by conventional methods. The isocyanates andisothiocyanates as employed herein may be prepared in known methods byre acting a suitable amine with phosgene (COCl and thi0- phosgene (CSCIrespectively.

V 8 I claim: 1. The phosphorohydrazidothioates corresponding to theformula wherein each R represents a member of the group con sisting oflower alkoxy and di(lower alkyl)-amino and represents a member of thegroup having the structures --NII-NHX NH-NX2 NX-NX2 and if NHNHC-NHZ inwhich X is selected from the group consisting of lower alkanoyl andbenzoyl, Y is selected from the group consisting of oxygen and sulfurand Z is selected from the group consisting of lower alkyl, loweralkenyl, cyclohexyl and phenyl.

2. 0,0-dimethyl 2-allylthiocarbamoyl phosphorohydra zidothioate.

3. 0,0-diethyl 2-cyclohexylthiocarbamoyl phosphorohydrazidothioate.

4. 0,0-diethyl 2-allylthiocarbarnoyl phosphorohydrazidothioate.

5. 0,0-diethyl Z-acetyl phosphorohydrazidothioate.

6. 0,0-dimethyl Z-phenylcarbamoyl phosphorohydrazidothioate.

No references cited.

1. THE PHOSPHOROHYDRAZIDOTHIOATES CORRESPONDING TO THE FORMULA